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Do vibrationally excited OH molecules affect middle and upper atmospheric chemistry?

Clarmann, T. von 1; Hase, F. 1; Funke, B.; Lopez-Puertas, M.; Orphal, J. 1; Sinnhuber, M. ORCID iD icon 1; Stiller, G. P. 1; Winkler, H.
1 Institut für Meteorologie und Klimaforschung (IMK), Karlsruher Institut für Technologie (KIT)


Except for a few reactions involving electronically excited molecular or atomic oxygen or nitrogen, atmospheric chemistry modelling usually assumes that the temperature dependence of reaction rates is characterized by Arrhenius’ law involving kinetic temperatures. It is known, however, that in the upper atmosphere the vibrational temperatures may exceed the kinetic temperatures by several hundreds of Kelvins. This excess energy has an impact on the reaction rates. We have used upper atmospheric OH populations and reaction rate coefficients for OH(υ = 0...9)+O3 and OH(υ = 0...9)+O to estimate the effective (i.e. population weighted) reaction rates for various atmospheric conditions. We have found that the effective rate coefficient for OH(υ =0...9)+O3 can be larger by a factor of up to 1470 than that involving OH in its vibrational ground state only. At altitudes where vibrationally excited states of OH are highly populated, the OH reaction is a minor sink of Ox and O3 compared to other reactions involving, e.g., atomic oxygen. Thus the impact of vibrationally excited OH on the ozone or Ox sink remains small. Among quiescent atmospheres under investigation, the largest while still small (less than 0.1%) effect was found for the polar winter upper stratosphere and mesosphere. ... mehr

Verlagsausgabe §
DOI: 10.5445/IR/1000039141
Veröffentlicht am 27.04.2018
DOI: 10.5194/acp-10-9953-2010
Zitationen: 6
Web of Science
Zitationen: 6
Zitationen: 8
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Meteorologie und Klimaforschung – Atmosphärische Spurenstoffe und Fernerkundung (IMK-ASF)
KIT-Zentrum Klima und Umwelt (ZKU)
Publikationstyp Zeitschriftenaufsatz
Publikationsjahr 2010
Sprache Englisch
Identifikator ISSN: 1680-7316, 1680-7324
KITopen-ID: 1000039141
HGF-Programm 12.04.03 (POF II, LK 01) Chem.Budgets u.Chemie-Klima-Wechselw.
Erschienen in Atmospheric chemistry and physics
Verlag European Geosciences Union (EGU)
Band 10
Heft 20
Seiten 9953-9964
Externe Relationen Abstract/Volltext
Nachgewiesen in Web of Science
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